WO2021033953A1 - Procédé de préparation d'un copolymère greffé constitué d'un composé cyanovinylique, d'un composé diène conjugué et d'un composé vinyle aromatique, et composition de résine thermoplastique comprenant le copolymère greffé - Google Patents

Procédé de préparation d'un copolymère greffé constitué d'un composé cyanovinylique, d'un composé diène conjugué et d'un composé vinyle aromatique, et composition de résine thermoplastique comprenant le copolymère greffé Download PDF

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WO2021033953A1
WO2021033953A1 PCT/KR2020/010185 KR2020010185W WO2021033953A1 WO 2021033953 A1 WO2021033953 A1 WO 2021033953A1 KR 2020010185 W KR2020010185 W KR 2020010185W WO 2021033953 A1 WO2021033953 A1 WO 2021033953A1
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weight
compound
parts
graft copolymer
conjugated diene
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PCT/KR2020/010185
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English (en)
Korean (ko)
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김유빈
석재민
정용환
박찬홍
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(주) 엘지화학
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Priority to CN202080006926.5A priority Critical patent/CN113260644B/zh
Priority to US17/299,218 priority patent/US20220049038A1/en
Priority to EP20854245.6A priority patent/EP3872104B1/fr
Publication of WO2021033953A1 publication Critical patent/WO2021033953A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/18—Increasing the size of the dispersed particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a method for preparing a graft copolymer and a thermoplastic resin composition comprising the graft copolymer, and more particularly, to a graft copolymer obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex.
  • Graft copolymer having excellent cohesion efficiency and excellent gloss, color, and processing characteristics by mixing and aging a nonionic polymer coagulant and cationic polymer coagulant, or a nonionic polymer coagulant and anionic polymer coagulant into the coalescence latex.
  • a thermoplastic resin composition containing the graft copolymer.
  • ABS-based copolymer represented by vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as "ABS-based copolymer”) has impact resistance, mechanical strength, moldability, and gloss It is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts due to its good physical properties such as degrees.
  • ABS-based copolymer when an ABS-based copolymer is prepared by grafting an aromatic vinyl compound and a vinyl cyan compound monomer to a conjugated diene-based rubber latex by emulsion polymerization, it shows a good balance of properties compared to the ABS-based copolymer prepared by bulk polymerization, and has excellent gloss, etc.
  • ABS-based copolymer is mainly produced by emulsion polymerization because it has the advantage of having.
  • ABS-based copolymer latex produced by emulsion polymerization is preferably processed into powder for reduction in volume, various utility, and ease of handling.
  • the ABS-based resin latex is agglomerated, aged, dehydrated and dried. ABS resin powder can be obtained.
  • the agglomeration of the ABS-based copolymer latex prepared by the emulsion polymerization can chemically agglomerate the latex particles stabilized by the emulsifier used in the emulsion polymerization by using various coagulants, and the coagulant is an acid or metal salt.
  • the coagulant is an acid or metal salt.
  • Aggregation of latex using an acid has a disadvantage in that the thermal stability of the ABS resin is lowered due to residual acid, and the amount of gas generated during the thermoforming process is large and the yellowness of the resin is high.
  • the aggregation of latex using a metal salt has a problem that the amount of gas generated and the yellowness are relatively low, but the productivity is low.
  • Patent Document 1 Korean Patent Registration No. 10-0463482
  • the substrate contains 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight.
  • Graft polymerization to prepare a graft copolymer latex And 0.04 to 0.27 parts by weight of a nonionic polymer flocculant as a first flocculant, and 0.47 to 1.65 parts by weight of a cationic polymer flocculant or 0.73 to 1.65 parts by weight of an anionic polymer flocculant as a second flocculant based on 100 parts by weight of the prepared graft copolymer latex (based on solid content).
  • the second coagulant is a cationic polymer coagulant
  • the total of the nonionic polymer coagulant and the cationic polymer coagulant is 0.7 to 1.7 parts by weight
  • the second coagulant In the case of anionic polymer flocculant, the total amount of the nonionic polymer flocculant and the anionic polymer flocculant is adjusted to 0.97 to 3.37 parts by weight, so that the aggregation efficiency is good, the gloss is excellent, and the b value measured using a Hunter Lab color meter
  • the present substrate is graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight.
  • the present disclosure provides a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer prepared by the above production method.
  • the present substrate is a thermoplastic comprising 20 to 40% by weight of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and 60 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer Provides a resin composition.
  • a graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex is agglomerated with a nonionic polymer flocculant and a cationic polymer flocculant, or a nonionic polymer flocculant and an anionic polymer flocculant, and
  • the aggregation efficiency is excellent, the b-value measured using a Hunter Lab color meter and the b-value measured after staying are low, and the glossiness is improved, so that the color is beautiful.
  • the present inventors agglomerated the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex with a nonionic polymer flocculant and a cationic polymer flocculant, or a nonionic polymer flocculant and an anionic polymer flocculant, but the polymer flocculant in a specific amount.
  • the gloss is high and the b value measured using a Hunter Lab color meter and the b value measured after staying at 250°C for 15 minutes (hereinafter referred to as "b value after staying") are low, so the color is excellent.
  • b value after staying the present invention was completed by further focusing on research.
  • a detailed method of preparing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer according to the present disclosure is as follows.
  • the production method of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure comprises 20 to 40% by weight of an aromatic vinyl compound and 20 to 40% by weight of an aromatic vinyl compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight.
  • the second coagulant is a cationic polymer coagulant
  • the total of the nonionic polymer coagulant and the cationic polymer coagulant is 0.7 to 1.7 parts by weight
  • the second coagulant is an anionic polymer
  • the total amount of the nonionic polymer coagulant and the anionic polymer coagulant is 0.97 to 3.37 parts by weight, and in this case, the coagulation efficiency is excellent, and the b value measured using a Hunter Lab color meter and the b value after stay are Excellent color due to low gloss It works.
  • the manufacturing method of the conjugated diene rubber latex is, for example, 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight modifier, and 0.1 to 1 part by weight of the initiator may be added and polymerized to prepare a conjugated diene rubber latex. In this case, there is an effect of excellent impact resistance.
  • the method for producing a conjugated diene rubber latex includes 100 parts by weight of a conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, 0.2 to 0.4 parts by weight of a molecular weight modifier. And 0.3 to 0.8 parts by weight of the initiator may be added and polymerized to prepare a conjugated diene rubber latex, and in this case, the impact resistance is excellent.
  • the method for preparing the conjugated diene rubber latex includes 30 to 100 parts by weight of ion-exchanged water, 0.3 to 2 parts by weight of emulsifier, 0.01 to 0.5 parts by weight of electrolyte, and molecular weight modifier in 75 to 90 parts by weight of 100 parts by weight of the conjugated diene compound.
  • Adding 0.1 to 0.5 parts by weight and 0.05 to 0.5 parts by weight of an initiator and performing primary polymerization; 0.05 to 0.5 parts by weight of an initiator and 10 to 25 parts by weight of a conjugated diene compound are continuously added to a polymerization conversion rate of 35 to 45% after the first polymerization step, followed by secondary polymerization; Adding 0.2 to 1 parts by weight of an emulsifier and performing tertiary polymerization at a point in which the polymerization conversion rate is 70 to 80% after the second polymerization step; After the tertiary polymerization step, terminating the polymerization at a polymerization conversion rate of 93 to 99% by weight; may include, and in this case, there is an effect of excellent impact resistance.
  • the polymerization conversion rate may be defined as the weight% of the monomer converted to the polymer until measurement based on 100% of the total weight of the monomers added until the polymerization is completed, and the method of measuring the polymerization conversion rate is determined according to this definition.
  • the method of measuring the polymerization conversion rate is not particularly limited, and as a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150° C. for 15 minutes, and then the weight is measured and the total solid content (TSC) is calculated by Equation 1 below. It can be obtained and calculated using Equation 2 below. Equation 2 is based on the total weight of the added monomer is 100 parts by weight.
  • Polymerization conversion rate (%) [Total solid content (TSC) X (total weight of added monomer, ion-exchanged water, and auxiliary raw materials) / 100]-(weight of auxiliary raw materials other than monomer and ion-exchanged water)
  • Sub-materials in Equation 2 refer to initiators, emulsifiers, electrolytes, and molecular weight modifiers.
  • the added monomer refers to a conjugated diene compound.
  • the conjugated diene compound is one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, for example It can be more than that.
  • the emulsifier may be, for example, one or more selected from the group consisting of rosin acid metal salts, alkyl aryl sulfonates, alkalimethyl alkyl sulfates, sulfonated alkyl esters, and metal salts of unsaturated fatty acids.
  • the electrolyte is for example KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , It may be at least one selected from the group consisting of Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4.
  • the initiator may be, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and the water-soluble persulfate polymerization initiator is, for example, a group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the oil-soluble polymerization initiator may be one or more selected from, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramethane hydroperoxide and benzoyl It may be one or more selected from the group consisting of peroxide, and examples of the oxidation-reduction catalyst system include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium pyrrolate. It may be one or more selected from the group consisting of sodium sulfate.
  • the conjugated diene rubber latex When preparing the conjugated diene rubber latex, it may be most preferably potassium persulfate.
  • the molecular weight modifier may be a mercaptans-based molecular weight modifier as an example, and in particular, tertiary dodecyl mercaptan is preferred.
  • the conjugated diene rubber latex of the present disclosure may be, for example, an average particle diameter of 1,800 to 5,000 ⁇ , preferably 2,000 to 4,000 ⁇ , more preferably 2,500 to 3,500 ⁇ , and has excellent impact resistance within this range.
  • the average particle diameter of this description is a sample prepared by diluting the conjugated diene rubber latex to a total solid content (TSC) of 0.1% or less, and then using a Nicomp TM 380 device (PSS, Nicomp, USA) by a dynamic laser light scattering method. It can be measured using.
  • the step of preparing the graft copolymer latex is, for example, grafting 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinylcyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. It is possible to perform graft polymerization, preferably 25 to 35% by weight of an aromatic vinyl compound and 5 to 15% by weight of a vinyl cyan compound in 55 to 65% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. And within this range, there is an effect excellent in impact resistance, mechanical strength and moldability.
  • the solid content is defined as the content of the active ingredient remaining when all the moisture in the latex has been evaporated.
  • Solid content (% by weight) 100-[(Weight of latex before moisture drying (g)-Weight of remaining powder after moisture drying (g)) / Weight of latex before moisture drying X 100]
  • the step of preparing the graft copolymer latex is, for example, a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound in a total of 100 parts by weight, ion exchange water 70 to 200 parts by weight, initiator 0.1 to 2 parts by weight, emulsifier 0.1 to After polymerization by adding 2 parts by weight and 0.05 to 1.5 parts by weight of a molecular weight control agent, the polymerization reaction may be terminated at a polymerization conversion rate of 93 to 99% by weight.
  • the polymerization conversion rate follows the definition and measurement method of the polymerization conversion rate described above in the preparation of the conjugated diene rubber latex, but the added monomer refers to a conjugated diene compound, an aromatic vinyl compound, and a vinyl cyan compound contained in the rubber latex.
  • the step of preparing the graft copolymer latex includes a total of 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound and a vinyl cyan compound, 100 to 170 parts by weight of ion exchange water, 0.3 to 1 part by weight of an initiator, and an emulsifier. 0.5 to 1.5 parts by weight and 0.1 to 1.0 parts by weight of a molecular weight modifier are added to perform the polymerization reaction, and the polymerization reaction can be terminated at a polymerization conversion ratio of 95 to 98% by weight.
  • the step of preparing the graft copolymer latex includes 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight based on a total of 100 parts by weight of a conjugated diene rubber, an aromatic vinyl compound, and a vinyl cyan compound, and ions.
  • the vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
  • the aromatic vinyl compound is, for example, styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ⁇ -brobo styrene, ⁇ -bro It may be one or more selected from the group consisting of parent styrene, m-bromo styrene, o-chloro styrene, ⁇ -chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene, and vinyl naphthalene.
  • the emulsifier, initiator, and molecular weight modifier may be used within the range used in the preparation step of the conjugated diene rubber latex, for example.
  • additives such as electrolytes not specifically mentioned in the present description, may be appropriately selected as needed, and are particularly limited if they are within the range generally applied to the production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex. It doesn't work.
  • reaction conditions such as reaction time, reaction temperature, pressure, and addition time of reactants in the method for preparing the graft copolymer are not particularly limited if they are within the range commonly used in the technical field to which the present invention belongs, and is necessary. It can be appropriately selected and implemented according to.
  • the graft copolymer latex prepared above is agglomerated and aged by a coagulant to form a graft copolymer slurry.
  • the agglomeration and aging step is, for example, 0.04 to 0.27 parts by weight of a nonionic polymer coagulant as a first coagulant, and 0.47 to 1.65 parts by weight of a cationic polymer coagulant as a second coagulant based on 100 parts by weight (based on solid content) of the prepared graft copolymer latex.
  • the second coagulant is an anionic polymer coagulant
  • the total of the nonionic polymer coagulant and the anionic polymer coagulant may be 0.97 to 3.37 parts by weight, and in this case, the coagulant is efficiently performed and the gloss is high and a Hunter Lab color meter is used. The measured b value and the b value after stay are low, so the color is beautiful.
  • the agglomeration and aging step may be, for example, a step of coagulating and aging by adding a first polymer coagulant and a second polymer coagulant to the graft copolymer latex at 75 to 90°C, and preferably, a first polymer coagulant and a second polymer coagulant. It may be a step of coagulating and aging by adding a polymeric coagulant at 78 to 82°C, in which case the coagulation is uniformly performed and the coagulation efficiency is excellent.
  • the agglomeration and aging step is carried out for 5 to 100 minutes, preferably 20 to 80 minutes, more preferably 30 to 60 minutes after adding the first polymer coagulant and the second polymer coagulant to the graft copolymer latex, for example.
  • the agglomeration and aging step is carried out for 5 to 100 minutes, preferably 20 to 80 minutes, more preferably 30 to 60 minutes after adding the first polymer coagulant and the second polymer coagulant to the graft copolymer latex, for example.
  • the agglomeration and aging step may be performed under conditions of, for example, a stirring speed of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm, but is limited thereto. no.
  • a stirring speed of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm, but is limited thereto. no.
  • productivity is excellent, aggregation efficiency is high, and physical property balance is excellent.
  • the nonionic polymer coagulant may be, for example, 0.04 to 0.27 parts by weight, preferably 0.05 to 0.25 parts by weight, and within this range, agglomeration is efficiently performed and the gloss is high and a Hunter Lab color meter is used. The measured b value and the b value after stay are low, so the color is beautiful.
  • the cationic polymer flocculant may be, for example, 0.47 to 1.65 parts by weight, preferably 0.5 to 1.6 parts by weight, more preferably 0.1 to 1.0 parts by weight, in which case the aggregation is efficiently performed and the glossiness is It is high and the b-value measured using a Hunter Lab color meter and the b-value after stay are low, so the color is beautiful.
  • the anionic polymer flocculant may be, for example, 0.73 to 3.35 parts by weight, preferably 0.75 to 3.3 parts by weight, and more preferably 0.75 to 1.5 parts by weight, in which case the aggregation is efficiently performed and the glossiness is It is high and the b-value measured using a Hunter Lab color meter and the b-value after stay are low, so the color is beautiful.
  • the total of the nonionic polymer coagulant and the cationic polymer coagulant may be, for example, 0.7 to 1.7 parts by weight, preferably 0.75 to 1.65 parts by weight, more preferably 0.75 to 1.2 parts by weight, , Aggregation is efficiently performed within this range, and the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so the color is beautiful.
  • the total of the nonionic polymer coagulant and the anionic polymer coagulant may be, for example, 0.97 to 3.37 parts by weight, preferably 1.0 to 3.35 parts by weight, more preferably 1.0 to 2.0 parts by weight, , Aggregation is efficiently performed within this range, and the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so the color is beautiful.
  • the cationic polymer flocculant may include, for example, an amino group, an ammonium group, or both at the end, and the anionic polymer flocculant may include, for example, an amide group, a carboxylate group, or both at the end, in this case Aggregation is made efficiently, and the gloss is high, and the b-value after stay measured using a Hunter Lab color meter is low, so the color is beautiful.
  • the cationic polymer flocculant may be one or more selected from the group consisting of a methacrylate polymer flocculant, an ammonium acrylate polymer flocculant, and an ammonium acrylamide polymer flocculant, and in this case, a high glossiness and a Hunter Lab color meter may be used.
  • the b value measured by using and the b value after stay is low, so the color is beautiful.
  • the cationic polymer flocculant may be, for example, a molecular weight of 0.01 to 10 ⁇ 10 6 Daltons, preferably 1 to 10 ⁇ 10 6 Daltons, and has excellent aggregation efficiency within this range.
  • the cationic polymer flocculant may be, for example, a pH of 0 to 5, preferably 1 to 4 in a 0.25 mass% solution, and has excellent flocculation efficiency within this range.
  • the cationic polymer flocculant may include, for example, a cationic polymer flocculant having a viscosity of 100 to 5000 cps in a 1% by mass stock solution, a molecular weight of 0.01 to 10 ⁇ 10 6 Daltons and a pH of 2 to 4 in a 0.1% by mass solution; A cationic polymer flocculant having a pH of 0-5 in a molecular weight of 0.01-10 ⁇ 10 6 Daltons and 0.25% by mass solution; Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.
  • the anionic polymer flocculant may be, for example, a molecular weight of 0.01 to 15 ⁇ 10 6 Daltons, preferably 1 to 15 ⁇ 10 6 Daltons, and has excellent aggregation efficiency within this range.
  • the anionic polymer flocculant may be, for example, a pH of 4 to 11, preferably 5 to 10 in a 0.25 mass% solution, and has excellent flocculation efficiency within this range.
  • the anionic polymer flocculant may include an anionic polymer flocculant having a viscosity of 1000 to 10000 cps in a 1% by mass stock solution, a molecular weight of 0.05 to 15 ⁇ 10 6 Daltons and a pH of 5 to 9 in a 0.1% by mass solution; Anionic polymer flocculant having a molecular weight of 0.01-15 ⁇ 10 6 Daltons and a pH of 5-10 in a 0.25 mass% solution; Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.
  • the nonionic polymer flocculant may be, for example, one or more selected from the group consisting of an acrylamide polymer flocculant, an ethylene oxide polymer flocculant, and a propylene oxide polymer flocculant.
  • an acrylamide polymer flocculant an ethylene oxide polymer flocculant
  • a propylene oxide polymer flocculant a high glossiness is used and a Hunter Lab color meter is used. The measured b value and the b value after stay are low, so the color has a beautiful effect.
  • the nonionic polymer flocculant may be, for example, a molecular weight of 0.05 to 10 ⁇ 10 6 Daltons, preferably 5 to 10 ⁇ 10 6 Daltons, and has excellent aggregation efficiency within this range.
  • the nonionic polymer flocculant may be, for example, a pH of 4 to 7.5, preferably 5 to 7 in a 0.25 mass% solution, or a pH of 3 to 8, preferably 4 to 7.5 in a 0.1 mass% solution, within this range. It has excellent cohesion efficiency.
  • the nonionic polymer flocculant is a specific example of a nonionic polymer flocculant having a viscosity of 100 to 4000 cps in a 1% by mass stock solution, a molecular weight of 0.05 to 10 ⁇ 10 6 Daltons and a pH of 4 to 7.5 in a 0.1% by mass solution; A nonionic polymer flocculant having a pH of 5-7 in a molecular weight of 0.05-10 x 10 6 Daltons and 0.25 mass% solution; Or a mixture thereof; in this case, the gloss is high and the b value measured using a Hunter Lab color meter and the b value after stay are low, so that the color is beautiful.
  • the viscosity can be measured using a Brookfield viscometer at room temperature (20-25°C) unless otherwise stated.
  • the molecular weight can be measured using gel permeation chromatography (GPC) unless otherwise stated.
  • the pH can be measured using a general pH measuring device at room temperature (20 to 25°C) unless otherwise stated, and specifically, it can be measured using the Thermo Scientific Orion Star A Series.
  • the polymer coagulant may be in the form of an emulsion, for example, a solid content of 0.1 to 10% by weight, emulsifier 1 to 20% by weight, dispersion stabilizer 0.1 to 10% by weight, and water may include 75 to 95% by weight, In this case, there is an effect of easy dispersion.
  • the solid content of the polymer coagulant may be, for example, 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 3 to 7% by weight, and in this case, there is an effect of easy dispersion.
  • an emulsion refers to a state in which two liquids that are not mixed with each other have a constant ratio and are dispersed in another liquid in the form of small droplets.
  • the weight thereof refers to the weight of the solid content excluding the solvent.
  • the agglomeration and aging step may further include an antioxidant, a stabilizer, or a mixture thereof, for example, and in this case, there is an effect of excellent balance of physical properties after extrusion.
  • the agglomerated graft copolymer latex can be obtained as a graft copolymer powder by dehydrating and drying, for example.
  • powder refers to an object in a state in which a large number of solid particles are aggregated, and for example, may be an object having an average particle diameter of 1 to 10,000 ⁇ m or 10 to 2,000 ⁇ m in a state in which a large number of solid particles are aggregated. .
  • the average particle diameter of the powder can be measured by the DP caking test.
  • 10 g of powder was compressed with a weight of 20 kg for 10 minutes, and then layered from #8 mesh (2380 ⁇ m) to #625 mesh (20 ⁇ m) on a sieve vibrator (Analysette 3) of Fritsch, Germany, and #625 mesh.
  • a sieve vibrator Analysette 3 of Fritsch, Germany, and #625 mesh.
  • the diameter of the particles passing through 50% by weight is taken as the average particle diameter of the powder.
  • the dehydration and drying step is not particularly limited if it is a method generally used in the art.
  • the slurry obtained after the agglomeration may be dehydrated using a centrifugal dehydrator, a compression dehydrator, or the like, to obtain a graft copolymer in a wet powder state.
  • the dehydration may be preferably performed one or more times, preferably 1 to 3 times, more preferably 2 to 3 times, in this case, and in this case, the residual emulsifier content is reduced to improve surface properties such as glossiness. Has the effect of being.
  • the graft copolymer in a wet powder state obtained after the dehydration has a moisture content of, for example, 40% by weight or less, preferably 10 to 40% by weight, more preferably 10 to 35% by weight or 10 to 30% by weight. %, and in this case, there is an advantage of excellent productivity by increasing the efficiency in the drying step, which is a post process.
  • the moisture content can be measured using a moisture analyzer, and specifically, a moisture analyzer of METTLER TOLEDO, Switzerland.
  • the drying is not particularly limited in the case of a known drying process commonly practiced in the technical field to which the present invention belongs, but as an example, the graft copolymer in a wet powder state is aired using a fluidized bed dryer. After supplying and drying, the graft copolymer powder can be obtained.
  • the graft copolymer powder obtained by drying the graft copolymer in the wet powder state may have a moisture content of 2% by weight or less, preferably 0.1 to 2% by weight, more preferably 0.1 to 1% by weight. And, within this range, there are advantages of excellent productivity of the copolymer and excellent physical properties such as mechanical strength, heat resistance, and surface gloss.
  • the moisture content can be measured using a moisture analyzer, and specifically, a moisture analyzer of METTLER TOLEDO, Switzerland.
  • the graft copolymer powder can be extruded after melt-kneading with an aromatic vinyl compound-vinyl cyan compound copolymer as an example, and in this case, it has excellent impact resistance, chemical resistance, molding processability and gloss, and a Hunter Lab color meter is used.
  • the measured b value and the b value after staying at 250° C. for 15 minutes are low, so that a thermoplastic resin composition having a beautiful color can be prepared.
  • the melt-kneading and extrusion step may be performed under 220 to 240° C. and 250 to 400 rpm, preferably at 225 to 235° C. and 300 to 400 rpm, but is not limited thereto.
  • the melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader, etc., and is not particularly limited.
  • melt-kneading for example, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight of at least one additive selected from the group consisting of a colorant, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a lubricant, a plasticizer, an antistatic agent, and a processing aid It can be input within the sub-range.
  • the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is characterized in that it is prepared by the above production method, and in this case, the b value and 250 measured using a Hunter Lab color meter After staying at °C for 15 minutes, the b value is low and the gloss is high, so the color is excellent. It works.
  • thermoplastic resin composition of the present invention is the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight, preferably 25 to 35% by weight and aromatic vinyl compound-vinyl cyan compound copolymer 60 To 80% by weight, preferably 65 to 75% by weight, and in this case, the agglomeration efficiency is excellent and the b value measured using a Hunter Lab color meter and measured after staying at 250°C for 15 minutes The low b value has a beautiful color effect.
  • the thermoplastic resin composition may have a glossiness of 80 or more, preferably 80 to 100, more preferably 80 to 93, measured at a 45° angle with a gloss meter according to ASTM D258, for example. , Within this range, there is an excellent effect of physical property balance and color.
  • the thermoplastic resin composition may have a b value of 4.9 or less, preferably 4.0 to 4.9, more preferably 4.6 to 4.9, measured using a Hunter Lab color meter as an example, and has excellent physical property balance and color within this range. It works.
  • the thermoplastic resin composition may have a b value of 8.3 or less, preferably 7.0 to 8.3, and more preferably 8.1 to 8.3, measured after staying at 250° C. for 15 minutes using a Hunter Lab color meter as an example, and within this range. The balance of physical properties and color are excellent.
  • thermoplastic resin composition is, for example, dissolved 0.3 g of the thermoplastic resin composition in chloroform, precipitated the polymer using methanol, filtered the supernatant, and then used the polymer flocculant into LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand). -alone instrument)
  • the content of the polymer flocculant measured using the equipment may be 4,000 ppm or less, preferably 100 to 4,000 ppm, more preferably 500 to 3,500 ppm, and within this range, there is an excellent effect of glossiness.
  • the molded article of the present disclosure is characterized in that it is manufactured from the thermoplastic resin composition, and in this case, it has excellent impact resistance, chemical resistance, molding processability and gloss, and at b-value measured using a Hunter Lab color meter and 250°C. The b value measured after staying for 15 minutes is low, so the color has a beautiful effect.
  • the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure Vinylcyan compound-conjugated diene compound-aromatic vinyl obtained by graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyanide compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight
  • a compound graft copolymer 0.3 g of the graft copolymer is dissolved in chloroform, the polymer is precipitated using methanol, the supernatant is filtered, and the polymer coagulant is used in LC/DAD Agilent 1290 LC-2 detectors (DAD and FLD as stand-alone instrument), the content of the polymer coagulant measured using the equipment is 10 to 15,000 ppm, and in this case, the b value measured using a Hunter Lab color meter and the b value after stay are low and the
  • the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer may have, for example, a polymer coagulant content of 10 to 15,000 ppm, preferably 300 to 13,000 ppm, more preferably 1,000 to 13,000 ppm, and this range
  • a polymer coagulant content 10 to 15,000 ppm, preferably 300 to 13,000 ppm, more preferably 1,000 to 13,000 ppm, and this range
  • the b-value measured using the Hunter Lab color meter inside the house and the b-value after stay are low and the color is excellent due to high glossiness. It works.
  • Cationic polymer flocculant HCP-800 from HANSOL CHEMICAL with a molecular weight of 1 to 10 ⁇ 10 6 Daltons, pH 0 to 5 in a 0.25 mass% solution
  • Anionic polymer flocculant HAP-606 from HANSOL CHEMICAL, having a molecular weight of 1 to 15 ⁇ 10 6 Daltons, pH 5 to 10 in a 0.25 mass% solution
  • Nonionic polymer flocculant HNP-910 from HANSOL CHEMICAL with a molecular weight of 5 to 10 ⁇ 10 6 Daltons and a pH of 5 to 7 in a 0.25 mass% solution
  • ion-exchanged water in a nitrogen-substituted polymerization reactor 85 parts by weight of 100 parts by weight of 1,3-butadiene as a monomer, 1.5 parts by weight of a fatty acid metal salt of C16 to C18 as an emulsifier, potassium carbonate as an electrolyte (K 2 CO 3 ) 0.15 parts by weight, 0.3 parts by weight of tertiary dodecylmercaptan (TDDM) as a molecular weight control agent, and 0.3 parts by weight of potassium persulfate as an initiator were put together, and polymerization was carried out at a reaction temperature of 70°C.
  • K 2 CO 3 potassium carbonate as an electrolyte
  • TDDM tertiary dodecylmercaptan
  • the prepared conjugated diene rubber latex had an average particle diameter of 3,000 ⁇ and a solid content of 55 to 60% by weight.
  • ABS graft copolymer Preparation of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer
  • the solid content prepared above is 55 to 60% by weight of conjugated diene rubber latex, 60 parts by weight and 100 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile and styrene mixed in a separate mixing device.
  • a mixed solution consisting of 30 parts by weight, 25 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosinate, and 0.35 parts by weight of tertiary dodecyl mercaptan, and 0.054 parts by weight of dextrose, pyrroleic acid 0.004 parts by weight of sodium and 0.002 parts by weight of ferrous sulfate were added together at 70° C. for 3 hours.
  • 0.05 parts by weight of a nonionic polymer coagulant and 1.6 parts by weight of a cationic polymer coagulant were added to 100 parts by weight of the ABS graft copolymer latex prepared above (based on solid content), and then coagulated and aged for 30 minutes.
  • the aggregated ABS graft copolymer was dehydrated and dried to prepare an ABS graft copolymer powder.
  • 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.
  • Example 1 was carried out in the same manner as in Example 1, except that the types and contents of the first coagulant and the second coagulant were changed as shown in Table 1 below.
  • ABS graft copolymer powder After adding 2.0 parts by weight of a cationic polymer coagulant to 100 parts by weight of the ABS graft copolymer latex prepared above (based on solid content) at 80°C, heating up to 93°C over 30 minutes to agglomerate the aggregated ABS graft copolymer Dehydration and drying were performed to prepare ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of an acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed into a mixer, and then melt-kneaded at 210°C using an extruder and pelletized, A specimen for measuring physical properties was prepared using an injection machine.
  • Comparative Example 1 except that the type and content of the coagulant was changed as shown in Table 2 below, it was carried out in the same manner as in Comparative Example 1.
  • Example 1 was carried out in the same manner as in Example 1, except that the types and contents of the first coagulant and the second coagulant were changed as shown in Tables 3 and 4 below.
  • Examples 1 to 4 according to the present invention have excellent cohesion efficiency, high glossiness, and low b value measured using a Hunter Lab color meter and low b value after staying. This was excellent.
  • Comparative Example 4 using 5.0 parts by weight of the anionic polymer flocculant alone decreased glossiness
  • Comparative Example 7 using 3.4 parts by weight did not aggregate
  • Comparative Example 5 using 5.0 parts by weight of the nonionic polymer flocculant alone Has deteriorated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un copolymère greffé, un copolymère greffé et un produit moulé en résine thermoplastique le contenant. Plus spécifiquement, la présente invention concerne un procédé de préparation d'un copolymère greffé et une composition de résine thermoplastique comprenant le copolymère greffé, le procédé comprenant : une étape de préparation d'un latex de copolymère greffé par polymérisation par greffage de 20 à 40 % en poids d'un composé vinyle aromatique et 1 à 20 % en poids d'un composé cyanovinylique sur 50 à 70 % en poids d'un latex de caoutchouc à diène conjugué ayant une teneur en solides de 30 à 65 % en poids ; et une étape de coagulation consistant à effectuer une coagulation par ajout, par rapport à 100 parties en poids du latex de copolymère greffé préparé (en termes de matières solides), 0,04 à 0,27 partie en poids d'un coagulant polymère non ionique en tant que premier coagulant, et en tant que second coagulant, 0,47 à 1,65 partie en poids d'un coagulant polymère cationique ou 0,73 à 3,35 parties en poids d'un coagulant polymère anionique. Lorsque le second coagulant est un coagulant polymère cationique, la somme totale du coagulant polymère non ionique et du coagulant polymère cationique est comprise de 0,7 à 1,7 partie en poids, et lorsque le second coagulant est un coagulant polymère anionique, la somme totale du coagulant polymère anionique et du coagulant polymère anionique est comprise de 0,97 à 3,37 parties en poids. Selon la présente invention, lorsque le procédé est utilisé pour préparer un copolymère greffé, le polymère greffé présente une excellente efficacité de coagulation et une brillance élevée. En outre, en raison d'une faible valeur b mesurée à l'aide d'un colorimètre HunterLab et d'une faible valeur b après rétention, ledit polymère greffé présente d'excellentes caractéristiques de couleur.
PCT/KR2020/010185 2019-08-16 2020-08-03 Procédé de préparation d'un copolymère greffé constitué d'un composé cyanovinylique, d'un composé diène conjugué et d'un composé vinyle aromatique, et composition de résine thermoplastique comprenant le copolymère greffé WO2021033953A1 (fr)

Priority Applications (3)

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CN202080006926.5A CN113260644B (zh) 2019-08-16 2020-08-03 乙烯基氰化合物-共轭二烯化合物-芳香族乙烯基化合物接枝共聚物的制备方法，和包含接枝共聚物的热塑性树脂组合物
US17/299,218 US20220049038A1 (en) 2019-08-16 2020-08-03 Method of preparing vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and thermoplastic resin composition including graft copolymer
EP20854245.6A EP3872104B1 (fr) 2019-08-16 2020-08-03 Procédé de préparation d'un copolymère greffé constitué d'un composé cyanovinylique, d'un composé diène conjugué et d'un composé vinyle aromatique, et composition de résine thermoplastique comprenant le copolymère greffé

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KR1020190100526A KR102489409B1 (ko) 2019-08-16 2019-08-16 비닐시안 화합물-공액디엔 화합물-방향족 비닐 화합물 그라프트 공중합체의 제조방법 및 이 그라프트 공중합체를 포함하는 열가소성 수지 조성물
KR10-2019-0100526 2019-08-16

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CN113121727B (zh) * 2021-04-13 2023-03-14 长春工业大学 一种abs接枝共聚物絮凝破乳的方法

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KR102489409B1 (ko) 2023-01-17
US20220049038A1 (en) 2022-02-17
CN113260644B (zh) 2023-03-28
EP3872104B1 (fr) 2024-05-01
EP3872104A1 (fr) 2021-09-01
EP3872104A4 (fr) 2022-03-16
CN113260644A (zh) 2021-08-13

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